Deactivation of poisons on contaminated cracking catalysts



' DEACTIVATION F rorsoNs 0N CONTAMI- NATED CRACKING CATALYSTS Albert N. De Vault, Bartlesville, Okla assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Filed Apr. 22; 1958, Ser No. 23 0,04 6

Claims. terms-426 This invention relates to the deactivation ofpoisons'on' contaminated cracking catalysts which have been used for conversion of hydrocarbon materials. In one of its aspectsythe invention: relates'to'the contacting jof a poisoned or used cracking catalyst with chromyl chloride 2 lz)- lates to the contacting'of a cracking catalyst at elevated temperature with chromyl chloride vapors. More ,specir fically, the invention relates to a catalytic operation m,

In another of its'aspects, the invention re nited States Patent A 2,946,740 n :Patentecl July 26, 1960 1 crease gasoline and other valuable liquid products yields 5 closure and its appended claims.

invention are apparent from a consideration by contacting the used catalystswith chromyl chloride.

Ordinarily the catalyst which is removed from the cracking zone and which has been stripped of residual vaporizable' hydrocarbon is' 'subjected to a regeneration operation' in the presence of controlled quantities of oxidizing gases'at'temperatures' which are well known in the art,

following which the regenerated catalyst is contacted with chromyl chloride. 'The contacting is conveniently effected at temperatures at which the catalyst is found following regeneration and just before it is conveyed to thecrackingzone- This temperature, though not limited which a catalyst is employed to crack a hydrocarbon and wherein the catalyst when ithas become fedked is -regenerated underregeneration conditions and wherein the catalyst at a'point inthe operation is'contacted with chromyl chloride vapors. V i

In the preliminary treatment of crudeoils' in their preparation as cracking stock there are performed certain conventional distillation operations. In these oper-f atio'ns there are obtained fractions of certain oils such as gas oil in which will be found concentrated a substan-: tial proportion of certain catalyst poisons which'are found in the original crude .oil. These poisonsinclude among others, certain compounds of nickel, vanadium, etc. These metal's'can'beipresnt as= inorganic salts but also can be present in certain combinations'or complexes of organiematerials. During the cracking operation, which as is well known is conductediat an elevated temperature, usually above approximately 7001 F., thevarithereto, can'be in the approximate range-of 700 to 1050" F. In a fixed bed unit the contacting can be effected by simply passing vapors of chromyl chloride over the regenerated bed of catalyst. In a fluid bed unit,

' the, treatment can be effected .by adding the treatingagent to the-catalyst in the transfer line which carries the re generated 1 catalyst to the reactor, or aside stream of regenerated -catalyst can be withdrawn from the reactor and/0r fromgthe regenerator, and this stream: can be atreated continuously or batch-wise and the thus treated catalyst returnedito the unit for use? in the cracking reaction. .Since any chromyl chloride added to the catalyst ultimately dccontaminate the same when the catalystreaches an elevated temperature it will be obvious tov .one skilled. in the art that chromyl chloride can rang ous metals contained in 'the' oil bifig coriverted"deposit on the'catalyst modifying'the'same to increase its capacity to produce hydrogen, dry gas and coke; To the extent that increased quantities of hydrogen, dry gas, coke and other undesirable materials are formed there is a corresponding loss of charge which can be converted to gasoline or other useful products. Furthermore, since most cracking units are limited in their charge rate by the regenerating capacity available for regenerating used or coked catalyst it will be seen that deactivation of the catalyst poisons responsible for increased coke formation is very highly desirable. Various processes or procedures have been set forth in the art for deactivation of metal contaminants upon hydrocarbon cracking catalysts. In one such operation, the catalyst, at operating temperature, is contacted with hydrogen chloride.

It has now been found that the contacting of used cracking catalyst, which is contaminated with metals and which contains these metals deposited on its surfaces, with chromyl chloride results in a marked decrease of carbon formation as well as a marked decrease in the formation of hydrogen and dry gas with a concomitant notable increase of gasoline. Obviously, to the extent that hydrogen, dry gas and coke formation are reduced the forma tion of gasoline and other valuable liquid products will be increased.

It is an object of this invention to deactivate poisons on contaminated cracking catalysts. -It is a further object or this invention to provide a process for the deactivation of metal contaminants on used hydrocarbon cracking catalysts. A still further object of the invention is to in- :be addedto thecatalyst at temperatures lower than those which-have beenlset, forth. The treating Ztemperature is, therefore, not critcial. Treatment at operating temper atur uch as those-encompassed in the approximate 885- 940 Eis now preferred. As noted,-'lowertemperature treatment, even an impregnation at. ordinary emperatures. is-guitt satisfactprysince' the treated: cata lyst is heated to operating temperatures by the time it is used in the reactor.

The amount of treating agent which is used is small. An amount ordinarily in the range of about 0.05 to about 1 weight percent of the catalyst, added continuously or intermittently to the catalyst as it passes a point in the operation is usually satisfactory.

One of the several important advantages obtained according to the process of the present invention is that of increasing unexpectedly the length of time during which chromyl chloride-treated catalyst will operate in a decontaminated manner in comparison with catalyst treated with the conventional hydrogen chloride.

EXAMPLE 13 minutes. The data are given in terms of 50 percent conversion. The catalyst employed was a silica-alumina crackingcatalyst made by' acid activation of a natural .clay. The catalyst had been removed from a toll sized cracking unit regenerator and was contaminated with 2,255 parts per million :of vanadium oxide and nickel oxide. As obtained from the regenerator, there was deposited 0.35 weight percent of coke on the catalyst. Regeneration was completed in the laboratory cracking unit lbefore carrying 'out the tests which are now described a In a first test,"the regenerated catalyst was treated at an operating temperature ,of 900 -F. with 0.26 :weight percent HCl (0.25 weight percent based onchlorine) and then used in a series of cracking cycles. 'In a second comparative test, another sample of the catalyst was treated with 0.66 weight per cent chromyl chloride (0.23 weight percent basedon chlorine). A third comparative testis shown without treatment.

ride islan effective cracking catalyst metal contaminant deactivator. 1 Furthermore, these data show that chromyl chloride is moreeffective than hydrogen chloride.

tained using-chlorine in the form of hydrochloric acid there is "obtained a marked reduction in the formation of hydrogen and dry There is also obtained a notable: reduction .of carbon formed on the catalyst. Thus averaging the carbon 'formed in the two cases a reduction of almost eight .percent of carbon formed is -'obtained.'

This is a very 'large'ireductiona's one skilled "in the-art" will agree.

.Since it is clear (that the the-exact nature. of the catalyst is-not critical in the sense thatva'rious cracking catalysts can be used according to I deed, in addition toia rather marked, longer lasting effect which is obtained using chromyl chloride than is obchromyl chloride function's togdeactivate the metalcon taminants upon the catalyst the invention to obtain the beneficialresults of the invention. Furthermore, the charge stock is not critical in the sense that it need only have the contaminants which deposit on the catalyst to permit the process of the present invention to be practiced.

Reasonable variation and modification are possible within the scope of the foregoing disclosure and the appended claims to the invention, the essence of which is that a used metal-contaminated cracking catalyst is contacted with i'eh'r'omyl chloride to deactivate the metal contaminant.

Icla'im: 7 4 v V 1. The deactivation of contaminants on contaminated cracking catalysts-which comprises contacting the same with chromyl chloride.

2. The deactivation of metal contaminants upon used hydrocarbon cracking catalysts which comprises contactin; the same at an elevated temperature with chromyl chloride in small amounts.

3. A process for cracking a-hydrocarbon such as gas oil, in the presence of a catalyst such as silica-alumina catalyst by acid activation of a natural clay, which comprises contacting said oil with said catalyst under crackingconditions, obtaining a stream of cracked prodnets and a contaminated catalyst, regenerating said catalyst to remove coke therefrom, then contacting the catalyst with phIOlIlYl chloride and then returning said catalyst for use :for afurther cracking of said oil.

'4. A-process according to claim 3 wherein the amount of chro nyl chloride used is in the range of 005-1 weight percent of the catalyst and the temperature is in the approximate range of 885-940 F. w

:5. A-process of detactivating contaminants on a conterminated silica-alumina hydrocarbon cracking catalyst which comprises contacting said catalyst with chromyl chloride-at aternperatureand for a time effective to cause deactivation of said contaminants with respect to further use of said catalyst for cracking of hydrocarbon.

References Citedin the tile ofthis patent ED STATES PATENTS 2,754,551 noheriy et al. Sept. '25, 1956 

5. A PROCESS OF DETACTIVATING CONTAMINANTS ON A CONTAMINATED SILICA-ALUMINA HYDROCARBON CRACKING CATALYST WHICH COMPRISES CONTACTING SAID CATALYST WITH CHROMYL CHLORIDE AT A TEMPERATURE AND FOR A TIME EFFECTIVE TO CAUSE DEACTIVATION OF SAID CONTAMINANTS WITH RESPECT TO FURTHER USE OF SAID CATALYST FOR CRACKING OF HYDROCARBON. 